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Synthesis Of Benzo[A]Pyrene And Derivatives: Labelling Of Positions 1, 2, 3, 11 And 12, Richard S. Bodine

Chemistry and Chemical Biology ETDs

The ketone, 3, 4-dihydrobenz[a]anthracen-1(2H)-one (1), was prepared in three steps from anthracene. Condensation of the lithioenolate of ethyl acetate with the ketone(1) in tetrahydrofuran at -78°C afforded ethyl (1-hydroxy-1, 2, 3, 4-tetrahydrobenz[a]anthracen-1-yl)acetate (2). Dehydration and dehydrogenation over palladium/charcoal provided ethyl (benz[a]anthracen-1-yl)acetate (3). Reduction of the ester (3) with diisobutylaluminum hydride in toluene at -75°C gave benz[a]anthracen-1-ylacetaldehyde (4) which was cyclized with methanesulfonic acid to benzo[a]pyrene (5). Saponification of the ester (3) gave benz[a]anthracen-1-ylacetic acid (6) which was cyclized with methanesulfonic acid to benzo[a]pyren-11-o1 (7). Oxidation of the phenol (7) with Fremy's salt afforded the quinone, 11, 12-dihydrobenzo[a]pyrene-11, 12-dione (8). Reduction …

A Simple Experiment Illustrating The Structure Of Association Colloids, Stig Friberg, Beverly Bendiksen

Chemistry Faculty Research & Creative Works

No abstract provided.

Pulling The Wool Off, Department Of Agriculture, Western Australia

Journal of the Department of Agriculture, Western Australia, Series 4

The Department of Agriculture has begun a three year project to study the potential for "chemical shearing" or, more correctly, biological defleecing.

A Polarographic Study Of Fe(Ii) And Fe(Iii) Complexes With Catechol, Wen-Tang Shen

Dissertations and Theses

A study of the anodic polarography of catechol in 0.100 F sodium perchlorate is presented. A new wave is observed in alkaline solutions which is different from the simple oxidation wave of catechol to ortho-quinone observed by previous workers. The importance of buffer materials is discussed and a possible explanation of the new wave is suggested.

A study of the polarography behavior of Fe(II) and Fe(III) in the presence of catechol is reported. In the case of reduction of Fe(III) in the presence of catechol, two steps occur at about -1.5 and -1.8 volts (vs. SCE) at pH higher than …

Esculin Hydrolysis In The Enterobacteriaceae, Jane Shigeko Okada

University of the Pacific Theses and Dissertations

Esculin hydrolysis, as mentioned earlier, is now a recognized test in the identification of Group P enterococci. However, its use as a taxonomic tool in differentiating the genera and species of Enterobacteriaceae has not been widely accepted, partly because of the conflicting reports in the literature and partly because of the availability of more reliable tests. Some commercial kits (MS-2, Abbott Laboratories, Dallas, Texas; Micro-Id General Diagnostics, Morris Plains, New Jersey), however, have incorporated it among their battery of biochemical tests.

The nature of the enzyme has not studied for bacteria other than the KES group and E.coli.

Because of …

I. Extracellular Metabolites From Coprinus Macrorhizus Microsporus. Isolation And Characterization Of Hydroxylagopodin B. Ii. The Cell Wall Composition And Structure Of Coprinus Macrorhizus Microsporus, Carey Bernard Bottom

Doctoral Dissertations

“A purple pigment excreted into the culture medium of a mutant strain of the basidiomycete, Coprinus macrorhizus var. microsporus (ATCC 34960) has been isolated and characterized as hydroxylagopodin B based on ultraviolet, infrared, and mass spectral data. A wild-type strain of C. macrorhizus microsporus does not produce the purple pigment, however it does produce lagopodin B which is yellow in solution. Identification of lagopodin B was based on its melting point, the purple color of its alkaline solution, the mass spectrum, and mobility equivalence with a standard by thin-layer chromatography. The production of hydroxylagopodin B in the mutant strain is …

Spectroscopic Study Of Ni(Ii)-4, 4’, 4’’, 4’ ’’ – Tetrasulfophthalocyanine In Aqueous Solution, Issa Ishaq Jabra

Masters Theses & Specialist Projects

It was determined spectrally that a monomer-dimer equilibrium exists in aqueous solutions of Ni-TSPC^4- over a concentration range of 5 x 10^-8 – 10^-4 M. Equilibrium measurements were made under natural ionic strength conditions at 29°, 39° and 49°C. The values obtained for the equilibrium constants at 29°, 39° and 49°C were 2.4 x 10⁸, 6.6 x 10⁷ and 2.9 x 10⁷ M^-1, respectively. These results indicated that the equilibrium strongly favors dimer formation. This study also showed that nickel is second to copper in enhancing the dimerization of metallotetrasulfophthalocyanine complexes. …

An Emulsion Dye Laser, Kenneth Lee Matheson, James M. Thorne

Faculty Publications

A laser dye which is insoluble in water has been dissolved in hexane and emulsified in a water matrix. When pumped with a nitrogen laser, this mixture was observed to lase. The emulsion is superior to a simple hexane solution because the excellent thermo-optical properties of the water matrix help prevent refractive-index gradients from degrading laser performance. This is a useful characteristic for flash-pumped dye lasers, laser-pumped dye lasers, and liquid filters. Another type of solvent system, a critical solution, is also discussed. For certain dyes, a critical solution has even better thermo-optical properties because of its ability to absorb …

[3H]‑Raffinose, A Novel Radioactive Label For Determining Organ Sites Of Catabolism Of Proteins In The Circulation, Jonathon Van Zile, Lee A. Henderson, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

The primary tissue sites of catabolism of plasma proteins with long circulating half-lives are unknown. It has been difficult to identify these sites because plasma proteins are delivered to tissues at relatively slow rates but are rapidly degraded intracellularly within lysosomes. Therefore, a tracer attached to protein is lost from the site of uptake before an amount sufficient for quantitation can accumulate. We hypothesized that sucrose (Glupal-2 /3Fruf) would be a useful label to circumvent this difficulty because of the stability of sucrose in lysosomes; and thus, sucrose should remain in tissue long after the protein to which it was …

20th Annual Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Abstracts and program from the 20th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 7-9, 1978.

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Electrogenerated Chemiluminescence Of Trans-Stilbene Derivatives, James R. Wilson

Chemistry and Chemical Biology ETDs

A group of 15 compounds, all structurally related to trans­stilbene have been studied in systems of electrogenerated chemiluminescence (ECL). The compounds are substituted 2-phenyl indenes, dihydronapthalenes, and dihydrophenanthrenes. Absorption and fluorescence spectra, fluorescence quantum yield, cyclic voltammetry, and ECL were obtained for each compound. The ECL experiments were set up as single and mixed systems which used tri­para-tolylamine as the source of cation radicals. Each mixed system was studied in two different solvents, which were acetonitrile and a 1:1 mixture of acetonitrile and benzene. Single systems were studied only in the acetonitrile-benzene solution. Emissions at wavelengths longer than the fluorescence …

The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley

WM Keck Science Faculty Papers

The disappearance of the exciting-wavelength dependence of the phosphorescence spectra of polar, aromatic chromophores in supercooled glycol–water mixtures is utilized to monitor the kinetics of solvent reorientation. Reorientation times in the nanosecond to second range are obtained for (3:2 v/v) glycerol–water and (1:1 v/v) ethylene glycol–water at 140–240 °K. The results suggest that the process is one involving a cluster of solvent molecules and in which the chromophore plays a relatively passive role. Steady-state data and direct measurements of phosphorescence shifts as a function of time indicate that the solvent reorientation process is nonexponential in nature. The decay function derived …

Chemiluminescence Studies Of Silicon Fluoride And Uranium Oxide, Russell A. Armstrong

Chemistry and Chemical Biology ETDs

Spectroscopic studies of the reactions of fluorine with silicon, silane and deuterated silane, and of oxygen with uranium are reported. Chemiluminescence and atomic absorption techniques have been employed to determine the kinetics, photon yields and branching ratios of the chemistry leading to the excited states of the radical SiF. The reaction of silicon vapor with fluorine occurs at nearly a gas kinetic rate (k₂=1.3 x 10^-10 cc molecule^-1 sec^-1). The overall system photon yield from the reaction of silane and fluorine to produce SiF(A➔X) and SiF(a➔X) emission were 5 x 10^-2% and …

Studies Toward The Synthesis Of A- And B- Mercapto Alanine Derivatives, And Of A,B- And B, B- Dimercapto Alanine Derivatives, Aldean James Kolar

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

A convenient, economical, large scale synthesis of N-acetyldehydro-alanine (a-acetamidoacrylic acid) and its methyl ester was developed via a sequence of N-chlorination-dehydrochlorination. The method was extended to the synthesis of the corresponding N-benzoyl, N-phenylacetyl and N-benzyloxycarbonyl derivatives.

The conversion of a-methoxy-N-acetyl alanine derivatives to the corresponding a-mercapto alanine derivatives, using zinc chloride and an appropriate mercaptan, was investigated. Methyl a-methoxy-N-acetyl-D, L-alaninate was successfully converted to the a-acetylthio derivative, in 24% yield; however, a 90% yield could be obtained by treatment of the dehydroalanine derivative with hydrogen chloride gas in neat thiolacetic acid.

A facile conversion of the a-acetylthio derivative to the …

Comparative Enzymology Of Glyoxalase I, Christina Margaret Schimandle

Chemistry and Chemical Biology ETDs

The role of the metal ion in rat erythrocyte glyoxalase I was evaluated. The apoenzyme was formed by dialysis against an EDTA-imidazole buffer. Fluorescence studies of the Mg⁺⁺- and Mn⁺⁺-dansylated glyoxalase I's suggest that the metal ion is near the active site of the enzyme and participates in the catalytic reaction. Stereochemical studies of the conversion of methylglyoxal to S-lactoylglutathione with Mg⁺⁺, Mn⁺⁺, Co⁺⁺ and Ni⁺⁺-glyoxalase I's show that the 0-lactate of S-lactoylglutathione (97±1.5%) is formed. This result suggests that the reaction mechanism is the same with a change …

Specificity Of Antisera Against Hordeum Vulgare Ribonuclease And Serological Quantitation Of The Enzyme In Tissue Extracts, Steven Bryan Hawthorne

Electronic Theses and Dissertations

Specific rabbit antisera against purified seedling RNase I from both a hardy (Dicktoo) and less-hardy (Tennessee Winter) cultivar of winter barley was obtained using a 1 mg injection schedule. Both antisera formed a single precipitin band on double immunodiffusion and immunoelectrophoresis when reacted with the homologous crude tissue extract. RNase antigen from either cultivar was highly cross-reactive with both antisera. Passive hemagglutination inhibition was used in an attempt to distinguish purified RNase from both cultivars. A consistent difference in anti-RNase serum specificity between cultivars was shown, but the difference observed by this method was not sufficient to conclude structural differences …

Amperometric Determination Of Chemical Oxygen Demand, Catherine Eckert Hutchins

Masters Theses

A method is described for measuring the low level --5 to 50 ppm-- chemical oxygen demand (COD) of water samples by amperometric titration. The method involves digestion of the sample with potassium dichromate in a 50% sulfuric acid solution using one-fifth the reagents and sample required for the standard COD method. This is followed by an amperometric titration using a standard ferrous ammonium sulfate solution and employing a rotating platinum electrode in a three-electrode potentiostatic system. The titration is carried out at a potential of +0.80 volts versus a saturated calomel electrode, thus eliminating the need for O₂ purging …

Ergosterol Effect On The Desaturation Of 14c-Cis-Vaccenate In Tetrahymena, Tiee-Chyau Miin

Masters Theses

Supplement of ergosterol to the growth medium of the ciliated protozoan Tetrahymena pyriformis W leads to incorporation of the foreign sterol within cell membranes and suppression of synthesis of the native sterol-like compound tetrahymanol, as well as to changes in the fatty acid compositions of several major classes of membrane lipid. Alteration of fatty acid composition is thought to represent a regulatory mechanism whereby optimum membrane fluidity is maintained when the slightly dissimilar foreign sterol is added into the phospholipid bilayer of the membranes.

The present study, using several different conditions of growth temperature, substrate concentrations and incubation time, and …

The Joy Of Chemistry- Personal Impressions (Text And Audio), Frank D. Starkey

Honorees for Teaching Excellence

No abstract provided.

Mechanism Of The Ninhydrin Reaction, Carey B. Bottom, Samir B. Hanna, Donald J. Siehr

Chemistry Faculty Research & Creative Works

No abstract provided.

Regulation Of Protein Synthesis In Rabbit Reticulocyte Lysates By The Heme-Regulated Protein Kinase: Inhibition Of Interaction Of Met-TrnaFMet Binding Factor With Another Initiation Factor In Formation Of Met-TrnaFMet.4os Ribosomal Subunit Complexes, R. S. Ranu, I. M. London, A. Das, A. Dasgupta, A. Majumdar, R. Ralston, R. Roy, N. K. Gupta

Department of Chemistry: Faculty Publications

Protein synthesis in reticulocytes and their lysates is regulated by heme. In heme deficiency a heme-regulated translational inhibitor (HRI) that blocks initiation of polypeptide chains is activated. HRI is a protein kinase (ATP: protein phosphotransferase, EC 2.7.1.37) that specifically phosphorylates the 38,000-dalton subunit of the Met-tRNA_f^Met indin factor (IF), which forms a ternary complex with Met- tRNA_f^Met and GTP, a finding that suggests that the inhibition by HRI involves the phosphorylation of IF. We have investigated the effect of HRI in the partial reactions of protein chain initiation in which the IF-promoted binding of Met-tRNA_{f …}

The Product Distribution And Structural Assignment Of The Monobromination Products Of 7-Hydroxy-2,2,5-Trimethylchroman-4-One, Marsha L. Dutkowski

Dissertations and Theses @ UNI

The compound 6-bromo-7-hydroxy-2,2,5-trimethylchroman-4-one (1) was desired for use in a project directed toward the synthesis of two novel depsidones. Since 7-hydroxy-2,2,5-trimethylchroman-4-one (2) was readily available, a number of bromination conditions were investigated in an attempt to find a regiospecific synthesis of 1. However, mixtures of varying composition of 1, 2, 3 and 4 were obtained under all the conditions tried. Final separation of 1 and its isomer 3 was accomplished by a mixture of chromatographic techniques. Structural assignment of the two brominated products 1 and 3 was made by a combination of carbon and proton NMR.

New Evidence Supporting The Assignment Of Glutamic Acid As An Iron Ligand In Hemerythrin, Patricia M. Gormley

Dissertations and Theses

The amino acid sequence determination of Phascolopsis gouldii hemerythrin in the region of the proposed iron ligand at position 58 was the main objective of this research endeavor. Generation of a large peptide was pursued by trypsin digestion of citraconylated hemerythrin producing peptide 50-113 for sequenator analysis. Detection of the phenylthiohydantoin amino acid derivatives by gas-liquid and high-performance-liquid chromatography yielded unambiguous sequence elucidation through the region of interest identifying residue 58 as glutamic acid.

Direct Determination Of Pentachlorophenol By Differential Pulse Polarography, Albert L. Wade

Theses and Dissertations

Concern over environmental contamination leading to the introduction of pentachlorophenol into human and animal systems has resulted in the need for a rapid and direct method for determining trace concentrations of this highly toxic compound. A direct electrochemical procedure has been developed for determining trace conccentrations of this phenol dovm to 0.27 ppm. This method uses the electrochemical techniques of differential pulse polarography at the dropping mercury electrode, and differential pulse voltammetry at the carbon paste electrode to reduce pentachlorophenol for this determination. Cyclic voltammetry at the hanging mercury drop electrode has been used to characterize the reaction behavior of …

Physical Studies Of Hg(Ii) And Ag(I) Dna Complexes, Dawen Ding

Chemistry and Chemical Biology ETDs

The binding of Hg(II) and Ag(I) to the bases of DNA and polynucleotides induces strong absorption and CD bands. From electric dichroism studies, the transition moment of the difference absorption band at 293 nm is in the plane of the bases and has a huge negative CD band at 285 nm; while the corresponding 293 nm difference absorption band of DNA-Ag(I) complex is relatively CD inactive. A second band at 270 nm in the difference absorption spectrum of the DNA-Ag(I) complex has a large associated CD band at 270 nm. This transition is out of the plane of the bases. …

Synthesis And Studies Of A Carbon-13 Labelled Chemical Carcinogen, Robert E. Royer

Chemistry and Chemical Biology ETDs

Derivatives of 6-methylbenzo[a]pyrene enriched to 90% carbon-13 at the methyl carbon were synthesized. Reactions of the carcinogen, 6-chloromethylbenzo[a]pyrene, with nucleophiles under solvolytic conditions were studied kinetically and, using labelled 6-chloromethylbenzo[a]pyrene, the reaction products were studied by CMR. The purpose was to characterize the selectivity of the benzo[a]pyrenyl- 6-methyl carbonium ion in its reactions with some simple nucleophiles and with nucleosides and other nucleic acid components.

Although the solvolysis of 6-chloromethylbenzo[a]pyrene in aqueous/organic solution is first order, information about the course of the reaction can be obtained, under certain circumstances, from rate constants. Thus, if the rate of solvolysis is slowed …

Photochemical Studies Of Hydroxo-Bridged Complexes Of Chromium (Iii), Ronald Raymond Ruminski

Chemistry and Chemical Biology ETDs

The acid solution and solid state photolysis in both visible and ultraviolet regions of the spectrum for µ-hydro­xo-bis[pentaamminechromium(III)] chloride, and the solution photolysis in the visible and 1 traviolet region of the spectrum for µ-hydroxo-bis[pentaarnrninechr rnium(III)] perchlorate, have been studied. The ultraviolet irradiation of µ-hydroxo-bis[pentaamminechromium(III)] chloride in HCl and CHlO₄ produces a redox photoproduct identified as HCrO₄^-, although the rate of production of HCrO₄^- in HClO₄ is slower than in HCl. Photochemical cleavage of the hydroxo-bridge occurs in the ultraviolet photolysis of µ -hydroxo-bis[pentaanuninechromium(III)] chloride and is 1.9 times faster than the corresponding …

The Effects Of Various Pyrolysis Conditions On The Release Of Products From Green River Oil Shale, Georgia Thomas Fritz

Chemistry and Chemical Biology ETDs

The fusion of oil shales with eutectic mixtures of inorganic salts was studied with the objective of finding a chemical means of releasing the organic material either at a lower temperature or with a lower empirical activation energy (E_a). Experimental techniques by which the pyrolysis of oil shale was studied were thermogravimetry (TG), evolved gas detection (EGD), and pyrolysis/thin-layer chromatography (TLC). The following fused salts were investigated (ratios in mo1%): LiCO₃/Na₂co₃/K2CO3, 43.5/31.5/25.0; KSCN/NaSCN, 73.75/26.25; KSCN/­NaSCN, 70/30; Na₂SO₄/K₂SO₄/ZnSO₄, 29.1/30.2/40.7; NaCl/Na₂CO_{3 …}

Determination Of The Rate Of Formation Of Hcn, Mitchell Hull

Honors Theses

Nitric oxide is a major air pollutant arising from fossil fuel combustion, yet the fuel contribution to its formulation is uncertain. Since, in combustion, fossil fuels undergo disintegration before oxidation takes place, the study of the pyrolsis of a model constituent of fossil fuels can shed light on NO formation. The rate of inert pyrolytic disappearance of pyridine and the rate of formation of the principal Nitrogen-containing pyrolytic product, HCN, was studied in an inert atmosphere. The rate constant for the formation of HCN and its temperature dependence were determined.